266 nm激光光解C2H5SSC2H5产物的激光诱导荧光光谱

引用本文: 郝海燕, 刘振, 祖莉莉. 266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱[J]. 物理化学学报, 2015, 31(11): 2029-2035. doi: 10.3866/PKU.WHXB201509231 shu

Citation: HAO Hai-Yan, LIU Zhen, ZU Li-Li. Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser[J]. Acta Physico-Chimica Sinica, 2015, 31(11): 2029-2035. doi: 10.3866/PKU.WHXB201509231 shu

266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱

1.
北京师范大学化学学院, 理论与光化学教育部重点实验室, 北京 100875

通讯作者: 祖莉莉

基金项目:
国家自然科学基金(21373033, 21173024)资助项目 (21373033, 21173024)

摘要: 有机硫化物是大气主要污染物之一, 其在大气中的光解产物还将造成二次污染, 除了存在于有机硫化物中, S―S键还存在于胱氨酸等蛋白质中, S―S键的形成和断裂决定该类蛋白质的活性. 本工作中, 我们研究了用实验室常见的Nd:YAG激光器的四倍频266 nm激光光解C₂H₅SSC₂H₅过程, 通过激光诱导荧光(LIF)光谱方法检测乙硫自由基C₂H₅S等光解产物. 实验表明266 nm激光主要光解C₂H₅SSC₂H₅的S―S键产生C₂H₅S自由基.本文应用密度泛函理论的Becke3-Lee-Yang-Parr 泛函(B3LYP方法)得到C₂H₅SSC₂H₅的S―S键、C―S键和C―C键的解离势能曲线, 可知在266 nm光解条件下, C₂H₅SSC₂H₅在基态能够发生S―S键、C―S键解离,C―C键不发生解离. 本文采用全活化空间自洽场(CASSCF)方法优化得到态和态的C₂H₅S自由基结构及其跃迁的绝热激发能, 以辅助解析实验检测的C₂H₅S自由基的LIF光谱. 实验结合理论计算最终得出, 本实验266 nm光解条件下, C₂H₅SSC₂H₅主要发生S―S键解离, 不排除少量分子发生C―S键解离的可能性.

关键词:

English

Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser

1.
Key Laboratory of Theoretical and Computational Photochemistry of the Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China

Corresponding author: 祖莉莉

Received Date: 20 July 2015
Fund Project:
国家自然科学基金(21373033, 21173024)资助项目

Abstract: Organic sulfides are an atmospheric pollutant that photolyze in the atmosphere, causing additional pollution. The S―S bond exists not only in organic sulfides but also in some proteins such as L-cystine, and this bond is crucial to the bioactivity of this protein. In this work, we studied C₂H₅SSC₂H₅ photolysis at 266 nm, which is the quadruplicated frequency of the common Nd:YAG laser. The laser-induced fluorescence (LIF) spectra detected the photolyzed products, C₂H₅S radical. Our results show that the C₂H₅S radical was mainly created by dissociation of the S―S bond in C₂H₅SSC₂H₅. We determined the potential energy curves of the S―S, C―S, and C―C bonds in C₂H₅SSC₂H₅ at the B3LYP/6-311++G(d,p) level, finding that photolysis at 266 nm caused the S―S and C―S bonds of C₂H₅SSC₂H₅ to dissociate at the ground ???2029-1??? state. Nevertheless, photolysis at 266 nm did not photolyze the C―C bond of C₂H₅SSC₂H₅. By optimizing the C_s geometry of the C₂H₅S radical at the ???2029-1??? state and the ???2029-2??? state, we determined the ???2029-2???-???2029-1??? adiabatic transition energy at the CASSCF/6-311++G(d,p) level, and then studied the LIF spectra of the C₂H₅S radical. The main pathway is dissociation of the S―S bond of C₂H₅SSC₂H₅, though the C―S bond in a few C₂H₅SSC₂H₅ molecules did dissociate.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱

通讯作者: 祖莉莉

English

Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser

Corresponding author: 祖莉莉

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